1. Field of the Invention
The present invention relates to novel nitromethylene compounds that exhibit activity as insecticides, acaricides, and fungicides. The invention also relates to insecticidal, acaricidal, and fungicidal compositions comprising such nitromethylene compounds.
2. Description of Related Art
Destruction by insects, acarids and fungi presents a serious problem to agriculture. A wide variety of field crops are in need of protection from fungi, acarids, and insects including such valuable crops as soybeans, corn, peanuts, cotton, alfalfa, rice and tobacco. In addition, vegetables, such as tomatoes, potatoes, sugar beets, carrots, peas, and the like, as well as fruits, nuts, ornamentals, and seed bed crops, such as apples, peaches, almonds, citrus fruit and grapes may also require protection from the ravages of such pests.
Consequently, the development of new, more effective pesticides including insecticides, acaricides, and fungicides represents an ongoing scientific activity. More particularly, the development of pesticides which are effective as both ovicides and larvicides are of interest.
Chemical Abstracts 108(19):163280d refers to alkyl phenylhydrazinecarboxylates said to be useful as acaricides. U.S. Pat. No. 4,725,302 refers to substituted phenylhydrazines and phenyloxadiazolinones said to be useful as pesticides. European Patent 0 067 471 refers to 7-substituted 2,3-dihydrobenzofurans said to be useful as pesticides or chemical intermediates. DerWent abstract 88-312695/44 refers to arylhydrazides of trifluoroacetic acid said to have fungicidal, bacteriocidal, acaricidal, and antiseptic activity. Chemical Abstracts 105(17):152686c refers to various phenylhydrazines said to have activity against insects and mites.
Certain nitromethylene compounds which show insecticidal and fungicidal properties have been described in the following references: CA 71:70292, CA 72:78682, CA 76:31221, CA 93:38256, CA 102:166449, CA 106:115102, and CA 113:190943.
U.S. Pat. Nos. 3,641,098 and 3,786,131 disclose α-(halo, cyano, nitro, and azido)-α-(alkanoyl, carboalkoxy [i.e., alkoxy carbonyl], amino and mono- and di-alkyl amino)-carbonyl-(unsubstituted and mono to penta alkyl and/or electronegative substituent [e.g., halo, nitro, cyano, trifluoromethyl, trifluoromethyl-, -mercapto, -sulfonyl and -sulfoxyl, alkoxy, alkyl sulfonyl and/or dimethylaminosulfonyl sulfonyl]-substituted) phenyl hydrazones and their corresponding alkali metal, alkaline earth metal and amine salts, which are said to possess pesticidal, especially acaricidal and insecticidal, properties and which can be produced by conventional methods.
U.S. Pat. No. 4,426,393 discloses arylhydrazo-aldoximes which, as such, as tautomers, and in the form of organic or inorganic salts thereof, are said to be active in preventing and treating infections of useful plants by fungi, and in immunizing plants against such infections.
U.S. Pat. Nos. 5,367,093 and 5,536,746 disclose compounds having the structural formulae
wherein:
X is a) phenyl; lower phenylalkoxy; phenoxy; or benzyl; or b) one substituent from group a) and one or more substituents selected from C1-C4 alkoxy; halogen; lower alkyl; and lower alkylthio; or c) along with the phenyl to which it is attached, forms a multiple fused ring heterocycle such as dibenzofuranyl;
Y is H, C1-C4 alkanoyl, C1-C4 haloalkanoyl, dialkoxyphosphoryl, alkylaminocarbonyl, haloalkylsulfonyl, or C1-C4 alkoxy carbonyl; and
R is H, C1-C6 alkyl, C1-C6 alkoxy, C3-C6 cycloalkoxy, haloalkyl, alkoxyalkyl, arylalkoxy, alkenyl, alkylthio, alkoxycarbonyl, alkylamino, heteroaryl, arylalkyl, haloalkoxy, aryloxy, or C3-C6 cycloalkyl; and
Z is O or S.
The compounds are effective for controlling mites, nematodes, rice planthopper, tobacco budworm, and southern corn rootworm. Methods for making these compounds are also set forth.
U.S. Pat. No. 5,567,723 discloses compounds having the structural formulae
wherein R is C1-C6 alkoxy or C1-C6 alkyl; R1 is fluorenyl, thienyl, pyridyl or thiazolyl, unsubstituted or substituted by one or more substituents selected from C1-C4 alkoxy, C1-C4 alkyl, C1-C4 alkylthio, halogen, C1-C4 haloalkyl and nitro; and R2 is C1-C6 alkyl, C3-C6 cycloalkyl, C1-C6 haloalkyl, C2-C6 alkenyl, or C2-C6 alkoxyalkyl. The compounds are effective for controlling mites and nematodes.
U.S. Pat. No. 6,093,843 discloses compounds having the formula:
wherein R is hydrogen or CO2CH(CH3)2, that are useful as intermediates in the preparation of the miticide bifenazate, methods for their preparation, and methods for the preparation of bifenazate.
U.S. Pat. No. 6,297,275 discloses a method for controlling fungi using a phenylhydrazine derivative compound of the formula:
wherein: X is phenyl, phenylalkoxy, phenoxy, or benzyl, alone or in combination with one or more halogen, alkyl, or alkylthio; Y is hydrogen, alkanoyl, haloalkanoyl, or alkoxy carbonyl; and R is hydrogen, alkyl, haloalkyl, alkoxy, haloalkoxy, or phenylalkoxy.
U.S. Pat. No. 6,706,895 discloses a compound having the formula:
wherein R1 is alkyl and R2 and R3 are independently selected aryl groups. Also disclosed is a method of making bifenazate using the compound as an intermediate.
Canadian Patent No. 1 177 851 discloses arylhydrazo-aldoximes which, as such, as tautomers, and in the form of organic or inorganic salts thereof, are said to be active in preventing infections of useful plants by fungi, and in immunizing plants against such infections.
Chinese Patent No. 1035660 discloses an agricultural germicide that is said to be able to inhibit the growth of fungus in Phycomycetes Oomycetes. It is said to be effective for plant diseases resulting from Phycomycetes fungus and the powdery mildew of crops resulting from Ascomycetes. The structural formula is:
wherein R1 and R2 are as defined in the specification. It is also disclosed that the compound and intermediates can prevent and cure diseases of crops resulting from Phycomycetes fungus and are also effective for downy mildew of cucumber.
U.K. Patent No. 1,160,648 discloses preparations for combating pests that comprise, as active principle, a nitrazone of the formula
or a salt of such a nitrazone, in which formulae R1 represents a phenyl radical, which may be substituted by a halogen atom or preferably an alkyl group containing 1-4 carbon atoms, —NO2 or preferably an alkoxy radical containing 1-4 carbon atoms or a chlorophenoxy radical or a CF3 radical, and R2 represents an alkyl radical containing 1-4 carbon atoms or a phenyl radical, which may be substituted in the same manner as R1, together with a carrier.
The disclosures of the foregoing are incorporated herein by reference in their entirety.